Resinous products



United States REWOUS PRODUCTS Herschel G. Smith, Wallingford, and Troy L. Cantrell, Drexel Hill, Pa., and John G. Peters, Audubon, N. 1.,

-- assignors to Gulf Oil Corporation, Pittsburgh, Pa, a

corporation of Pennsylvania No Drawing. Application July 17, 1952, Serial No. 299,502

37 Claims. (Cl. 252-42-7) invention wherein mineral oil soluble, metal and sulfur containing, permanently thermoplastic, resinous materials are obtained by condensing in an aqueous medium, an alkylated monohydric phenol having at least one free reactive position in the nucleus, at least one alkyl group of such alkylated phenol containing at least 4 carbon atoms, formaldehyde and an alkali metal sulfide, at least one mol of formaldehyde being employed for every two mols of the phenol, and at least one equivalent of the alkali metal sulfide being employed for every two mols of the phenol.

The invention also includes the use of an alkali metal hydroxide or alkaline earth metal hydroxide in place of some of the alkali metal sulfide in the foregoing condensation, in which case suflicient alkali metal sulfide is employed in relation to the alkali metal hydroxide or alkaline earth metal hydroxide to yield not less than about 0.5 per cent by weight of sulfur in the final resinous product. The total amount of metal compound employed, that is, the amount of alkali metal sulfide plus alkali metal hydroxide or alkaline earth metal hydroxide remains in the proportion of at least one equivalent of total metal compound for every two mols of the phenol.

' The invention further includes the production of metal resinous compounds, other than the alkali metal compounds, by metathesis of any of the alkali metal resinous compounds obtained as described above with a water soluble salt of a metal other than an alkali metal.

The resinous products obtained in accordance with this invention are excellent additives for various mineral oil compositions and the invention also contemplates such compositions.

In preparing the metal and sulfur containing resins of our invention, it is necessary not to permit substantial reaction between the phenol and formaldehyde in the absence of the alkali metal sulfide and the alkali metal or alkaline earth metal hydroxide, if these hydroxides are employed. Accordingly, it is preferred to mix all of the ingredients and react them simultaneously. However, the alkali metal sulfide and formaldehyde, with or without the hydroxides, can first be mixed and partially reacted followed by addition of the phenol to the reaction mass and further reaction; or the alkali metal sulfide and phenol, with or without the hydroxides, can

atent Q first be reacted followed by reaction with the formaldehyde.

The condensation reaction of our invention takes place spontaneously at room temperatures, but it is preferred to employ moderately elevated temperatures in order to obtain reasonably rapid reaction rates. When the reaction sequence of first reacting the phenol and alkali metal sulfide and then reacting the formaldehyde is followed, the phenol and alkali metal sulfide, with or without the hydroxides disclosed, can be reacted first at temperatures as high as 400 F. Thereafter, for the subsequent reaction with formaldehyde, the reaction mass is cooled to, say F. to F, to avoid excessive volatilization of formaldehyde. In an instance where formaldehyde is present in the reacting mass, whether initially or otherwise, it is desirable not to exceed a reaction temperature of about 2002l0 F. in order to avoid loss of formaldehyde, although this loss can be reduced to some extent, when employing temperatures higher than about 210 F., by the use of closed reaction vessels.

Since the formaldehyde is most conveniently used in the form of commercial aqueous formalin containing 37 per cent by weight of formaldehyde, sufficient water for the reaction is generally'contained in the formalin solution. However, the alkali metal sulfides and the alkali metal and alkaline earth metal hydroxides may be conveniently dispersed and/ or dissolved in water to form an aqueous slurry or solution even when formalin is used.

In order to obtain the oil-soluble metal and sulfur containing resins of our invention, at least one mol of formaldehyde must be used for every two mols of the phenol. Amounts of formaldehyde less than this tend to yield oil-insoluble resins. Amounts of formaldehyde in excess of the amounts stated can be employed, since any formaldehyde in excess of the amount reacted is either volatiiized ed in the reaction or in the subsequent dehydration of the resin.

When alkali metal or alkaline earth metal hydroxides are employed in place of some of the alkali metal sulfide, it is necessary to use such an amount of hydroxide that the sulfur content of the resulting resin, which is derived of course from the alkali metal sulfide, does not fall below about 6.5 per cent by weight. This amount of sulfur in the product gives more effective bearing corrosion-inhibiting properties to a mineral lubricating oil compounded with the product than can be obtained with smaller amounts of sulfur. At the same time, the use of an alkali metal or alkaline earth metal hydroxide along with an alkali metal sulfide, in accordance with our invention, insures the obtaining of an additive which does not objectionably stain or blackcn silver bearing metals when incorporated in a mineral lubricating oil. In general, in order to obtain the desired minimum amounts of sulfur in the product while avoiding objectionable blackening of silver bearing metals, it is preferred that the relative molar proportions of alkali metal sulfide to alkali metal hydroxide or alkaline earth metal hydroxide, as the case may he, should be about 1:1. The use of an alkali metal monosulfide is also preferred. Lt should be understood, however, that the relative proportions stated are approximate and will vary, depending on whether an alkali metal monosulfide or polysulfide is employed and also on Whether an alkali metal or alkaline earth metal hydroxide is employed. t should be further understood that the total amount of metal compounds, that is, alkali metal sulfide with or without an alkali metal or alkaline earth metal hydroxide, is employed in the proportion of at least one equivalent of metal compound for every two mols of the phenol.

After the condensation reaction described above is completed, the temperature is raised to distill ofif all water, both that formed in the condensation and added with the reactants, to dehydrate the product. This or any other dehydration step conventional in the formation of resinous phenol-formaldehyde condensation products can be employed. Although the condensation reaction can be carried out solely in an aqueous medium, when the resinous product is to be used as a mineral oil additive, it is advantageous to use in addition a light naphtha solvent or a mineral lubricating oil of the same general type as the oil to which the resin is to be added. There is then obtained, after dehydration, a concentrate of the resin in solution in the naphtha or mineral lubricating oil, as the case may be. These concentrates are convenient for incorporating the additive into mineral oils.

The phenolic compounds employed in preparing our new resins are alkylated monohydric phenols having at least one alkyl group of at least 4 carbon atoms. As will be understood by those skilled in the art, such phenols must have at least one reactive position in the nucleus which is free of substituents. The presence of at least one alkyl group of at least 4 carbon atoms in the phenol insures oil solubility of the resinous condensation products prepared therefrom. Phenols not containing such group tend to yield products which are insoluble in mineral lubricating oils.

The alkylated phenols can readily be prepared by alkylating phenol or the simple monohydric homologues thereof, such as the naphthols, cresols, and ethyl and propyl phenols, with an alkyl halide or an alkanol in the presence of a Friedel-Crafts catalyst. Alternatively, alkylation can be performed with an olefin in the presence of concentrated sulfuric acid as a catalyst. The alkyl halides, alkanols and olefins employed in these alkylation reactions contain at least 4 carbon atoms and are selected to yield such alkyl radicals as butyl, amyl, heptyl, octyl, nonyl, decyl, stearyl and cetyl. The long chain alkyl groups derived from parafiin wax are also suitable; these yield the so-called wax phenols. Alkyl substituents containing from 4 to 12 carbon atoms form a preferred class. The alkylation reactions described are conventional and need not be further elaborated here.

Representative alkyl phenols of the class described include n-butyl phenol; sec-butyl phenol; tert-butyl phenol; Z-tert-butyl, 4-methyl phenol; 2,4-di-tert-butyl phenol; 2,6-di-tert-butyl phenol; Z-tert-butyl, 4-ethyl phenol; n-amyl phenol; di-tert amyl phenol; hexyl phenols; heptyl phenols; n-octyl phenol; iso-octyl phenol (alpha, alpha, gamma, gamma tetramethylbutyl phenol); nonyl phenol; decyl phenol; tri-isobutyl phenol; wax phenols; etc. Particularly good results have been obtained with tetramethylbutyl phenol.

The alkali-metal sulfides contemplated by this invention include the monoand polysulfides of sodium, potassium, lithium, rubidium and caesium. Monosulfides are preferred. Furthermore, because of their relative cheapness and availability, the sodium sulfides are preferred. When polysulfides are employed, the amount of sulfur combined into the final resinous product is increased, and the specific amount of sulfur in the final product can be controlled in part by the use of mono-, di-, tri-, tetraand pcnta-sulfides, as desired. Mixtures of the monosulfide and specific polysulfides can be employed to obtain sulfur contents falling within the amounts obtained by the use of any one sulfide. As has been disclosed hereinabove, further control of the amount of sulfur incorporated into the final product can be achieved by the use of alkali metal or al taline earth metal hydroxide in place of part of the alkali metal sulfide.

When it is desired to use an alkali metal or alkaline earth metal hydroxide in lieu of part of the alkali metal sulfide, the sodium, potassium, lithium, etc. alkali metal hydroxides, and the calcium, barium, strontium and magnesium alkaline earth metal hydroxides are suitable.

When avail, the corresponding oxides of the alkali and alkaline earth metals can be used in place of the hydroxides.

As has been stated heretofore, metal resinous compounds other than the alkali metal compounds can be prepared by metathesis of an alkali metal resin compound with a water soluble salt of such other metal. Thus an alkali metal containing resin is first prepared in the manner disclosed, i. e., by the condensation of formaldehyde, an alkylated phenol and an alkali metal sulfide with or without an alkali metal hydroxide or alkaline earth metal hydroxide, and then such alkali metal containing resin is reacted with the desired water soluble metal salt to achieve a double decomposition reaction. Preferably, the metathesis reaction is conducted prior to dehydration of the alkali metal resin, and dehydration is accomplished after methathesis. In this manner, metal containing resins can be readily prepared containing such metals as the alkaline earth metals (i. e., calcium, barium, strontium and magnesium) tin, copper, lead, zinc, manganese, cadmium, beryllium, silver, mercury, aluminum, bismuth, antimony, vanadium, chromium, iron, cobelt and nickel. Any of the nitrate, sulfate, chloride or alcoholate salts of the above metals which are appropriately water soluble can be used. If desired, part of the alkali metal can be retained in the product by employing less than stoichiometrical amounts of the water soluble metal salt in the metathesis reaction. It will be obvious from the foregoing that resins containing more than one metal can be prepared, and the invention also contemplates such resins.

The following examples are illustrative of the preparation of our new resins, and are not intended to limit the invention.

Example l.--lnto a vessel equipped for agitation, heating and cooling, there were charged 840 parts by weight of tetramethylbutyl phenol and 260 parts by weight of a 60 per cent by weight aqueous solution of sodium monosulfide. The mixture was heated to 350 F. with stirring and held at that temperature for 2 hours. Thereafter, the mixture was cooled to 160 F. and 340 parts by weight of a 37 per cent by weight aqueous solution of formaldehyde were slowly added with stirring. The mixture was then agitated at 180 F. for half an hour. The temperature was then raised to 300 F. to dehydrate the product, and stirring was continued while cooling to 160 F. At this point there were added 3000 parts by weight of Stoddard solvent and the solution obtained was filtered. The filtrate was charged to a vacuum stirring still, and the solvent distilled off under a vacuum of 379 mm. at a maximum pot temperature of 300 F. The residue was then placed in an evaporating dish and heated to 400 F. in an atmosphere of carbon dioxide to remove the last traces of solvent. The sodium and sulfur containing resin obtained had the following properties:

Color Dark amber. Sp. G12: 77/60 F 1.1941. Sulfur: Percent 5.51.

Ash as sulfate: Percent 5.93. Melting Point: F 164.

Example II .Into a reaction vessel there were charged 2 mols of sodium disulfide and 4 mols of formaldehyde in the form of a 37 per cent by weight aqueous formalin solution. These materials were heated to a temperature of 160 F. for 1 hour and then 4 mols of tetramethylbutyl phenol dissolved in 1100 grams of a light lubricating oil (154 S. U. S. at F.) were added. The reactants were heated to a temperature between about and F. for a period of 2 hours with agitation. Thereafter, 1 mol of aluminum sulfate was added and the temperature raised to ZOO-220 F. for a period of 2 hours with stirring. Following this, an additional 1100 grams of the light lubricating oil was added and the mixture was allowed to cool to 100 F. The aluminum salt of the condensation product thus formed was then dehydrated by raising the temperature to 280 F distilling off all water, both that added with the reactants and formed in the reaction. The mineral oil solution of the resin thus prepared had the following properties:

Example III.Into an enamel lined reaction vessel there were charged 1 mol of sodium monosulfide and 2 mols of formaldehyde in the form of a formalin solution. These were agitated for 1 hour at 160 F. Thereafter, there was added to the mixture 2 mols of tetramethylbutyl phenol in solution in 619 grams of the same light mineral oil as used in Example 11. The temperature was then maintained for 2 hours at 160-170 F. with stirring. Thereafter 1 mol of stannous chloride was added and the temperature raised to ZOO-220 F. where it was maintained for 2 hours. Following this an additional 619 grams of the same light mineral oil was added and the mixture cooled to 100 F. The tin salt of the condern sation product thus formed was then dehydrated by rais' ing the temperature to 280 F. The product was then filtered. The mineral oil solution of the product thus prepared had the following properties:

Gravity: API 16.2 Viscosity, SUS:

210 F 89 Color, ASTM Union 7.0 Sulfur, ,B: Percent 2.9 Neutralization No 20.9 alk. Ash as sulfate: Percent 9.1

Example lV.Into a reaction vessel there were charged 420 parts by weight of tetrarnethylbutyl phenol, 1000 parts by weight of the same light lubricating oil as in Example 11 and 130 parts by weight of a 60 per cent by weight aqueous solution of sodium monosulfide. The mixture was agitated and heated to a temperature of 210 F. for 1 hour after which it was cooled to 150 F. Thereafter an additional 1000 parts by weight of the lubricating oil and 170 parts by weight of a 37 per cent by weight aqueous solution of formaldehyde were added and the mixture heated with agitation at 190 F. for 2 hours. Following this, 140 parts by weight of calcium chloride dissolved in water were added to the mixture. The mixture was then dried by heating to a temperature of 280 F. and filtered. The mineral oil solution of the calcium and sulfur containing resin thus prepared had the following properties:

Gravity: API 2.17 Viscosity, S. U. 'S.: V

210 F 81.7 Color, ASTM Union 4.5 Sulfur, B: per cent 0.98

Neutralization No; 16.63 alk. Ash as sulfate: per cent 4.06

Example V.Into a reaction vessel equipped with means for agitation, heating and cooling, there were charged 306 parts by weight of tetramethylbutyl phenol, 400 parts by weight of a light lubricating oil (70 S. U. S. at 100 F.), 26 parts by weight of sodium monosulfide and 201 parts by weight of barium hydroxide octahydrate. Heat was applied to melt the phenol and 148 parts by weight of a 37 per cent by weight aqueous formaldehyde solution were slowly added while maintaining .aternperature of 160 F.- After being held at 160 F. for half an hour, the temperature was slowly raised to 310 F. to dehydrate the product, and thereafter a partial vacuum was applied for 15 minutes at this temperature to complete the drying. Thereafter, 450 parts by weight of the same light lubricating oil were added and the whole was filtered through diatomaceous earth. The filtrate, consisting of a concentrated solution of a sodium, barium and sulfur containing resin in the .lubrieating oil, had the following properties:

Gravity: API 10.1 Viscosity, S. U. 8.:

210 F 65.0 Color, ASTM Union 4.0 dil. Sulfur, B: per cent 0.53 Ash as sulfate: per cent 12.4

Example VI.-Into a reaction vessel there were charged 840 parts by weight of tetramethylbutyl phenol, 348 parts by weight of sodium tetrasulfide dissolved in water and 1100 parts by weight of a light lubricating oil (70 S. U. S. at F). The mixture was heated to 350 F. with stirring and held there for 2 hours. After cooling to 160 F., 340 parts by weight of formalin were slowly added and the mixture agitated at 180 F. for half an hour. Thereafter, the product was dehydrated by raising the temperature to 300 F. After cooling to 200 F., a solution in water of 244 parts by weight of BaClaZHzO was added, the mixture agitated and again heated to 300 F. to dry it. Then 1100 parts by weight of the same light lubricating oil were added and the solution filtered through diatomaceous earth. The concentrate of additive in the mineral oil had the following properties:

Gravity: API 9.7 Viscosity, S. U. 8.:

210 F 70 Color, ASTM Union 5.5 Ash as sulfate: per cent 10.31 Sulfur: per cent 1.04 Neutralization value ASTM D 97448 T Total Base No 29.5

Example VlI.-There were charged into a reaction vessel 880 parts by weight of tetramethylbutyl phenol and 1025 parts by weight of a 70 S. U. S. at 100 F. lubricating oil. The mixture was heated to F. to obtain a clear solution of the phenol 'in the oil, and then 65 parts by weight of a 60 per cent by weight aqueous solution of sodium monosulfide were added followed by heating to 220 F. for half an hour. Thereafter 473 parts by weight of dry barium hydroxide octahydrate were added and the mixture was heated to 350 F. with agitation. After cooling to F., 340 parts by weight of formalin were slowly added with agitation. The temperature was then raised to F. and held there for 1 hour. The mass was then dehydrated by heating to 300 F. and diluted with an additional 1025 parts by weight:

The product was then filteredof the same lubricating oil. through diatomaceous earth, the resulting solution of resin in the lubricating oil having the following properties:

While the above examples have illustrated the use of tetramethylbutyl phenol, the preferred phenol, other monohydric alkylated phenols, as disclosed herein, can be used with good results. Similarly, other alkali metal sulfides, other alkali metal or alkaline earth metal hydroxides, and other water soluble salts for the metathesis,

reaction can be employed in place of those shown in the examples.

The metal and sulfur containing resinous products of our invention are excellent addition agents for various mineral oils. They are readily soluble in all types of mineral lubricating oils, that is, parafiinic, naphthenic or mixed base oils and can be blended with them in high proportions. This excellent solubility of our new products enables the preparation of concentrated solutions thereof, as shown in the foregoing examples, which may then be diluted with additional oil to the proportions desired in the final mineral oil composition. These new addition agents confer excellent detergent effects and rust inhibiting properties on the mineral lubricating oils with which they are incorporated, and generally confer excellent bearing corrosion inhibiting properties on the oils containing them. For these purposes our new addition agents are added to mineral lubricating oils in minor amounts, say from about 0.1 to about 25 per cent by weight of the oil, suflicient to confer improved detergent properties on the oils with which they are incorporated. Generally the addition of about 1 to 2 per cent by weight of our new resins is sufiicient to effect the desired improvement, but for heavy duty applications larger amounts are employed.

Our new resins are not only useful in mineral lubricating oils but can be added to various mineral oils and compositions thereof to improve them in one or more respects. Thus, our new resins can be added to gasolines to retard haze formation and to distillate fuel oils to retard sludge formation. Because of their rust inhibiting properties, our new resins can be added to various volatile and non-volatile petroleum solvents and compositions to obtain improved coating compositions and slushing oils. Our new resins can also be employed in various lubricating greases. For the stabilization of fuels such as gasoline, diesel fuels and distillate furnace oils, small amounts as low as 0.001 per cent by weight of our resins can be employed, but somewhat larger amounts, from 0.01 to 5 per cent by weight, are preferable. Even larger amounts can be used, if desired, without harmful effect. The amount of resin to be used for the preparation of coating compositions containing mineral oils will vary with the nature of the coating required, but in general from about 0.1 to about 25 per cent of the resin will give satisfactory results.

From the foregoing it will be observed that the new resins of our invention are added to mineral oils in amounts ranging from 0.001 to 25 per cent by weight, depending on the nature of the mineral oil and the improvement desired, as will be apparent to those skilled in the art.

The following examples illustrate the use of our new resinous products to obtain improved mineral oil compositions.

Example VIlI.A highly refined lubricating oil was treated with 2 per cent by weight of the additive prepared according to Example I. A comparison of the base oil and the improved oil showed:

Example IX.A highly refined lubricating oil was treated with 6.0 per cent by volume of the mineral oil solution of the resin prepared according to Example H. A comparison of the base oil and the improved oil showed:

Base Oil gfl Gravity, API 29.8. Viscosity, S. U. 8.:

210 F... 68.0. Color, AS'IIVI Union 2.5. Neutralization No 0.11 alk Ash as Sulfate, percent 0.31. Engine Test, CRO L-4:

Engine Condition Rating iailtidt to com- 89.

p e e. Bearing Loss, MgJWhole Bearing ..do 6.

Example X.-A highly refined lubricating oil was treated with 6.0 per cent by volume of the mineral oil solution of the resin prepared according to Example III. A comparison of the base oil and the improved oil showed:

Base Improved Oil Oil Gravity, API 29.1..... 28.9. Viscosity, S. U.

"E 67.5"..- 68.0. Color, ASTM Umon.... 2.0 2.5. Neutralization No nil- 0.2 alk. Ash as Sulfate, per 0.4. Engine Test, CRO L-4:

Engine Condition Rating 94. Bearing Loss, Mg./Whole Bearing 69.

Example XI.An improved motor lubricating oil was prepared by treating a motor lubricating oil base with 6 per cent by volume of the mineral oil solution of the resin prepared according to Example IV. Comparative tests of the untreated oil and the treated oil follow:

Base on gf Gravity, API. Viscosity, S. U

210 F" Viscosity Index. Oolor, ASTM Union.... Appearance Sulfur, B, percent Precipitation No Copper Strip Test, 212 F., 3 Hr Corrosion Test, ASTM D 665-46 T:

Distilled Water- Steel Rod, Appearance Area Rusted, percent Centrifuge Test. Separation, percent:

,500 R. P. M., Room Temp., 2 Hr. Neutralization No Ash as Sulfate, percent Engine Test, ORG L-4:

Engine Condition Rating Bearing Loss, Mg./Whole Bearing.....

nil. passes.

bright. 0.

nil.

1.04 elk. 0.14.

failed to complete. .do

Example XII.An improved lubricating oil for the lubrication of diesel engines was prepared by treating a highly refined lubricating oil base with 12 per cent by volume of the mineral oil solution of the resin prepared according to Example V. Comparative tests of the base oil and the improved oil showed:

treated with '6 per cent by volume of the additive prepared according to Example VI. A comparison of the base oil and improved oil showed:

Example XIV.--A highly refined lubricating oil was treated with 12'per cent by volume of the additive solution prepared according to Example Vll. A comparison of the base oil and improved oil showed:

Base Improved Oil Oil Gravity, API 24. 8 22. 9 Viscosity, S. U. 8.:

100 F 1, 218 1, 109 210 84. 6 79. 6 Color, ASTM Un1on. 3. 25 5.

ulfur, B, Percent 0.18 0.21 Neutralization Value:

ASTM D 97448 T- Total Acid N o 0.06 Total Base No.. 4. 63 Ash as Sulfate, Percent 1.587 Falox Wear Test:

500 Lb. Gauge Load, 15 Min.

Wear, N o. of Teeth 10 0 Gauge Load at Seizure, Lb. Engine Test, CRC L-4:

Engine Condition Rating Bearing Loss, Mg./Whole Bearing H 0 The haze-inhibiting effect of the resins of our invention in gasoline is shown in the following table wherein the additive of Examples I and VII were added to a finished leaded gasoline in the proportion of 40 pounds of resin (dry basis) per 1000 barrels of gasoline:

As shown in the above examples, our new addition agents confer effective detergent properties on mineral lubricating oils. Thus the over-all rating and the engine condition ratings shown under the CRC L-4 engine tests indicate the freedom from engine deposits obtained. As shown by the date under hearing loss in these tests, which indicates the amount of bearing corrosion expressed in milligrams loss in weight of a standard bearing, the new resins tested confer excellent bearing corrosion inhibiting properties.

As shown under the U-V light stability tests for gasoline compositions containing the resins of our invention, a marked retardation in haze formation is obtained.

While we have shown in the examples lubricant and fuel compositions containing certain resins, our invention is not to be taken as limited to such resins, but comprises all of such materials within the purview of this disclosure. Furthermore, the invention is not limited to the use of our metal and sulfur containing resins in the preparation of compounded lubricating oils but comprises all mineral oil lubricants containing our new agents, such as greases and the like. As is known in the lubricating art, other additives in addition to the resins of our invention can be employed. These are materials such as pour point depressants, viscosity index improvers, antifoam agents, antioxidants, coloring materials, thickeners and the like.

Furthermore, as has been shown hereinabove our new resins can be added to a wide variety of mineral oils ineluding lubricating oils, gasoline, distillate fuels, furnace oils, light naphthas, slushing oils, etc.

Resort may be had to such modifications and variations as fall within the spirit of the invention and the scope of the appended claims.

We claim:

1. The process of preparing an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product which comprises condensing in an aqueous medium reactants consisting essentially of formaldehyde, an alkali metal sulfide and an alkylated monohydric phenol having at least one free reactive position in the nucleus, at least one alkyl group of such alkylated phenol containing at least 4 carbon atoms, at least one mol of formaldehyde being employed for every two mols of the phenol, and at least one equivalent of alkali metal sulfide being employed for every two mols of the phenol, the condensation being conducted to avoid any substantial reaction between the phenol and formaldehyde in the absence of the alkali metal sulfide.

2. The process of claim 1, wherein the condensation is carried out in a mineral oil, and there is recovered a solution of the resinous reaction product in the mineral oil.

3. The process of claim 1, wherein the metal and sulfur containing resin obtained is subjected to metathesis with a water soluble salt of a metal other than an alkali metal.

4. The process of preparing an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product which comprises condensing in an aqueous medium reactants consisting essentially of formaldehyde, an alkali metal sulfide, a compound selected from the group consisting of alkali metal and alkaline earth metal hydroxides and oxides, and an alkylated monohydric phenol having at least one free reactive position in the nucleus, at least one alkyl group of such alkylated phenol containing at least 4 carbon atoms; at least one mol of formaldehyde being employed for every two mols of the phenol, the relative amount of alkali metal sulfide and hydroxide or oxide being such as to yield a resin containing at least about 0.5 per cent by weight of sulfur, and at least one equivalent of the total of alkali metal sulfide and hydroxide or oxide being employed for every two mols of the phenol, the condensation being conducted to avoid any substantial reaction between the phenol and formaldehyde in the absence of the alkali metal sulfide and the hydroxide or oxide.

5. The process of claim 4, wherein the alkali metal sulfide and hydroxide are in the relative molar proportions of 1:1.

6. The process of claim 4, wherein the metal and sulfur containing resin obtained is subjected to metathesis with a water soluble salt of a metal other than an alkali metal.

7. The process of preparing an oil soluble, metal and sulfur containing, permanently thermoplastic condensation product which comprises condensing in an aqueous medium reactants consisting essentially of formaldehyde, an alkali metal monosulfide and tetramethylbutyl phenol, at least one mol of formaldehyde being employed for every two mols of the phenol, and at least one equivalent of alkali metal sulfide being employed for every two mols of the phenol, the condensation being conducted to avoid any substantial reaction between the phenol and formaldehyde in the absence of the alkali metal monosulfide.

8. The process of claim 7, wherein the alkali metal and 11 sulfur containing resin obtained is subjected to metathesis with a water soluble salt of stannous tin.

9. The process of claim 7, wherein the alkali metal and sulfur containing resin obtained is subjected to metathesis with a water soluble salt of an alkaline earth metal.

10. The process of claim 9, wherein the alkaline earth metal is barium.

11. The process of claim 9, wherein the alkaline earth metal is calcium.

12. The process of preparing an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product which comprises condensing in an aqueous medium reactants consisting essentially of formaldehyde, an alkali metal monosulfide, an alkaline earth metal hydroxide and tetramethylbutyl phenol, at least one mol of formaldehyde being employed for every two mols of the phenol, the relative amounts of alkali metal monosulfide and alkaline earth metal hydroxide being such as to yield a resin containing at least about 0.5 per cent by weight of sulfur, and at least one equivalent of the total of alkali metal sulfide and alkaline earth metal hydroxide being employed for every two mols of the phenol, the condensation being conducted to avoid any substantial reaction between the phenol and formaldehyde in the absence of the alkali metal monosulfide and alkaline earth metal hydroxide.

13. The process of claim 12, wherein the alkaline earth metal hydroxide is barium hydroxide.

14. An oil soluble, metal and sulfur containing per manently thermoplastic, resinous condensation product obtained by the process of claim 1.

15. A mineral oil solution of an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 2.

16. An oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 3.

17. An oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 4.

18. An oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 6.

19. An oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 7.

20. An oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 8.

21. An oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 9.

22. An oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 12.

23. A mineral oil composition comprising a major amount of a mineral oil and a minor amount, from about 0.001 to 25 per cent by weight, of an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 1.

24. A mineral oil composition comprising a major amount of a mineral oil and a minor amount, from about 0.001 to 25 per cent by weight, of an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 3.

25. A mineral oil composition comprising a major amount of a mineral oil and a minor amount, from about 0.001 to 25 per cent by weight, of an oil soluble, metal and sulfur containing, permanently thermoplastic,

resinous condensation product obtained by the process of claim 4.

26. The composition of claim 23, wherein the mineral oil is a lubricating oil.

27. The composition of claim 23, wherein the mineral oil is gasoline.

28. The composition of claim 23, wherein the mineral oil is a distillate fuel oil.

29. A lubricant composition comprising a major amount of a mineral lubricating oil, and a minor amount, sufiicient to confer improved detergent properties, of an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 1.

30. A lubricant composition comprising a major amount of a mineral lubricating oil, and a minor amount, sufficient to confer improved detergent properties, of an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 3.

31. A lubricant composition comprising a major amount of a mineral lubricating oil, and a minor amount, sufficient to confer improved detergent properties, of an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 4.

32. A lubricant composition comprising a major amount of a mineral lubricating oil and a minor amount, sufiicient to confer improved detergent properties, of an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 6.

33. A lubricant composition comprising a major amount of a mineral lubricating oil and a minor amount, sufficient to confer improved detergent properties, of an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 7.

34. A lubricant composition comprising a major amount of a mineral lubricating oil and a minor amount, sufficient to confer improved detergent properties, of an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 8.

35. A lubricant composition comprising a major amount of a mineral lubricating oil and a minor amount, sufficient to confer improved detergent properties, of an oil soluble metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 9.

36. A lubricant composition comprising a major amount of a mineral lubricating oil and a minor amount, sufficient to confer improved detergent properties, of an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 12.

37. A lubricant composition comprising a major amount of a mineral lubricating oil and a minor amount, suflicient to confer improved detergent properties, of an oil soluble, metal and sulfur containing, permanently thermoplastic, resinous condensation product obtained by the process of claim 13.

References Cited in the file of this patent UNITED STATES PATENTS 2,342,099 Ashley Feb. 22, 1944 2,361,804 Wilson Oct. 31, 1944 2,377,955 Mixon June 12, 1945 2,619,459 Neff Nov. 25, 1952 2,619,460 Neff Nov. 25, 1952 

1. THE PROCESS OF PREPARING AN OIL SOLUBLE, METAL AND SULFUR CONTAINING, PERMANENTLY THERMOPLASTIC, RESINOUS CONDENSATION PRODUCT WHICH COMPRISES CONDENSING IN AN AQUEOUS MEDIUM REACTANTS CONSISTING ESSENTIALLY OF FORMALDEHYDE, AN ALKALI METAL SULFIDE AND AN ALKYLATED MONOHYDRIC PHENOL HAVING AT LEAST ONE FREE REACTIVE POSITION IN THE NUCLEUS, AT LEAST ONE ALKYL GROUP OF SUCH ALKYLATED PHENOL CONTAINING AT LEAST 4 CARBON ATOMS, AT LEAST ONE MOL OF FORMALDEHYDE BEING EMPLOYED FOR EVERY TWO MOLS OF THE PHENOL, AND AT LEAST ONE EQUIVALENT OF ALKALI METAL SULFIDE BEING EMPLOYED FOR EVERY TWO MOLS OF THE PHENOL, THE CONDENSATION BEING CONDUCTED TO AVOID ANY SUBSTANTIAL REACTION BETWEEN THE PHENOL AND FORMALDEHYDE IN THE ABSENCE OF THE ALKALI METAL SULFIDE. 